Divinyl sulfone derivatives useful for rendering cellulosic textile fabric crease-resstant



States e This invention relates to textile chemicals and treatments of textiles therewith to improve the crease resistance of fabrics. More particularly, this invention is directed to novel sulfone derivatives characterized by a considerable lessening of irritational factors or odors normally characteristic of other sulfones, e.g., divinylslufones, and which are considerably less volatile and generally easier to handle in the textile mill.

Divinyl sulfones have heretofore been employed in the treatment of textiles to impart thereto wet and dry crease resistance. D. L. Schoene and V. S. Chambers describe such treatments in their US. Patents Nos. 2,539,704 and 2,524,399. These textile treatments with divinyl sulfones have not been acceptable to the textile industry because of the innate difficulties in handling and using noxious divinyl sulfones.

An object of this invention, therefore, is the provision of sulfone derivatives suitable for treating textile fabrics to impart improved crease resistance.

A further object is to provide novel textile chemicals of the vinyl sulfone type which chemicals, nevertheless, are substantially free of the objectionable vapors inherent in divinyl sulfones.

A further object is the provision of novel compositions which are useful in the treatment of textile fabrics for imparting wet and dry crease resistance thereto.

An additional object is to provide a novel process for the treatment of textile fabrics employing said novel divinyl sulfone derivatives.

Further objects and advantages of this invention are evident in the following detailed description.

The novel textile chemicals of this invention are the beta-(vinyl sulfonyl) ethyl diethers of glycols (wherein the vinyl and ethyl groups can have one additional substituent in the alpha or beta position) obtained by the reaction of substantially two moles or more of a divinyl sulfone with a dihydric aliphatic alcohol, e.g., an alkylene glycol or a polyoxyalkylene glycol. Illustratively, diethers of this invention are represented by the formula:

wherein R is alkylene of one to four carbon atoms or an oxyalkylene chain of an average molecular weight not greater than one thousand and in which the alkylene units can be the same or diiferent but have from one to four carbon atoms per unit; R is an alkylene group of one to four carbon atoms; 11 is zero to one; and R and R are alkyls of one to six carbon atoms, phenyl or hydrogen but when R on one carbon atom is alkyl or phenyl then R on the adjacent carbon atom is hydrogen and when R on one carbon atom is alkyl or phenyl then R on the adjacent carbon atom is hydrogen, the R groups being the same or dilferent and the R groups being the same or different in a single molecule.

The divinyl sulfone reactant can be substituted or un substituted and, when substituted, has only one substituent or" not more than six carbon atoms on each vinyl group. The divinyl sulfone reactant also includes the his (vinyl- 3,36,123 Patented Dec. 11, 1962 1 R: R3 0 u R2 R3 wherein R R R and n are as previously defined. Examples of divinyl sulfone reactants include divinyl sulfone (vinyl sulfone); dipropenyl sulfone (propenyl sulfone); di-isopropenyl sulfone (isopropenyl sulfone); 1,2- bis (vinylsulfonyl) ethane; 1,4-bis (vinylsulfonyl) butane; bis (vinylsulfonyl) methane; distyryl sulfone (styrylsulfone); bis (alpha-ethylvinyl) sulfone; bis (alpha-npropylvinyl) sulfone; bis (l-butenyl) sulfone; bis (alphaphenylvinyl sulfone and the like.

The glycol reactant preferably has a molecular weight of not more than one thousand and includes the alkylene glycols and the polyalkylene glycols. Examples of glycols are ethylene glycol; propylene glycol; butylene glycol; polytrimethylene glycol; polyethylene glycol 600; polypropylene glycol; mixed polyethylene-polypropylene glycol and the like. Illustratively, the formula, HOROH, wherein R is defined as above, represents glycols which are suitable for reaction with the divinyl sulfone reactants.

The process of making the novel compositions of this invention is carried out by mixing the divinyl sulfone and glycol reactants in a molar ratio of at least about 2 moles of sulfone per mole of glycol. An exothermic reaction is initiated under alkaline conditions, e.g., by adding an alkaline material such as sodium hydroxide to the mixture. The exothermic reaction is allowed to proceed to completion at which point approximately one-half of the vinyl groups are reacted as determined by analyzing samples of the reaction mixture. It is important to control the reaction temperature, as by cooling, in order to avoid the formation of insoluble by-products. The maximum temperature at which the reaction can be conducted without the formation of undesirable by-products will vary depending on the particular reactants used and the lowest possible temperature commensurate with a practical reaction speed will be used. In general, a reaction temperature of not greater than 60 C. provides an adequate speed of reaction. After about one half of the vinyl groups of the sulfone remain, the reaction mixture comprising the beta (vinylsulfonyl) ethyl diether of the glycol is preferably stabilized against further reaction by neutralizing it. Any unreacted divinyl sulfone reactant can be removed by sparging with an inert gas or by any other suitable means.

in selecting the reactants, the higher molecular weight reactants provide higher molecular weight products which when applied to fabrics require a higher degree of loading or pick-up than the product from lower molecular weight reactants to give the same degree of crease resistance. Thus, the selection of the reactants depends upon the weight of pick-up desired on the fabric or the type of hand desired for the fabric and the degree of crease resistance desired. Similarly, as the molar ratio of the divinyl sulfone reactant to the glycol reactant is reduced towards one, the average molecular weight of the diether product increases and the crease-proofing ability on a weight basis decreases. The maximum crease-proofing ability of the product per unit weight of product is obtained when it is made from approximately two moles of the divinyl sulfone per mole of glycols at molar ratios of divinyl sulfone to glycol substantially above two, an excess of divinyl sulfone remains in the product and can be moved by spar'ging or other suitable means.

The divinylsulfonylethyl diethers of glycols of this invention are applied to cellulosic textile fabrics from an aqueous solution (or a solution in a solvent capable of penetrating cellulosic fabrics) containing an alkaline cata lyst such as sodium bicarbonate, borax, and the like. The concentration of the diether is not narrowly critical and, for example, can be applied in a to 30 weight percent aqueous solution. The amount of alkaline catalyst also is not narrowly critical but should be sufficient to maintain the fabric in an alkaline condition during subsequent curing. For example, 0.1 to 5 wei ht percent of the catalyst is generally sufficient. After application of the aqueous diether solution the fabric preferably is squeezed to provide the desired pick-up which also is not narrowly critical and can range, for example, from 50 to 130 weight percent. The impregnated fabric is then dried and cured at elevated temperatures, e.g., 130 C. to 230 C. The length of time for adequate curing, for example, can be from one minute to five minutes.

Fabric treated in this manner has a high wet and dry crease resistance which persists even after many launderings and pressings. Although the thus treated fabric is useable, it has the disadvantage of low resistance to ageing and tenderizes or discolors under moist heat conditions or steaming. when the fabric treated in the above manner is further treated with aqueous caustic, potassium hydroxide or other strong alkali, or with other materials able to react with vinylsulfone groups, such as, sodium sulfite, with or without heating, the fabric after the usual Washing and bleaching is wet and dry crease resistant, is resistant to ageing and does not tenderize or objectionably discolor under moist heat conditions.

Wet crease resistant fabrics can be obtained by treating the textile fabric with the other diether solution followed by treatment with caustic or other alkali, or the fabric can be first treated with caustic or other alkali and then treated with the diether solution. After treatment with the diether solution and caustic the fabric is washed and dried and has a high degree of wet crease resistance but no significant improvement in dry crease resistance. Alternatively the diether and the caustic or other strong alkali can be applied to the fabric simultaneously.

The following examples are presented. in these examples all percentages are on a weight basis and all refiectances were measured with a Photovolt refiectorneter using a blue filter. Vinylsulfonyl group quantitative analyses were made in accordance with the well known sulfite method for determining formaldehyde as described in Formaldehyde by Walker, second edition, published by Reinhold Fublishing Corporattion. Crease resistance measurements are presented as the sum of the crease recovery angles for warp and filling as obtained from a Monsanto tester in accordance with AATCC Tentative Test Method 66-1959.

EXAMPLE 1 Diethylene Glycol Di(Bcta-(Vilzylsulfonyl)Ethyl) Ether A mixture was prepared from 472 grams (4 moles) of divinylsulfone and 212 grams (2 moles) of diethylene glycol. The mixture was cautiously neutralized by addition of 0.73 gram potassium hydroxide. An exothermic reaction in and the temperature of the mixture was held below 50 C. by cooling. After about 2 hours the reaction slo. ed down considerably and the mixture was left standing overnight and then stabilized by adding acetic acid to adjust the pH to 4.1. The product thus obtained was analyzed for vinylsulfonyl groups and was found to contain approximately one-half the amount of said groups in the original mixture. The product, diethylene glycol di(bcta(vinylsulfonyl)ethyl) ether, was soluble in water, had only a slight irritating odor and was considerably less, noxious than divinyl sulfone.

An 80 x 80 white cotton fabric, bleached and mercerized, was padded with an aqueous solution containing 150 grams of the diether as prepared above and 5 grams sodium carbonate per liter. The solution had a pH of set It has been found unexpectedly that 11.0. The pickup Was The padded fabric was allowed to dry at room temperature and then cured at 160 C. for 68 seconds, washed, dried, and pressed. it had a wrink.e recovery angle of 251 and a reflectance of 74.1%. Eiaillllg in a solution containing 1 g./l. available chlorine at pH 10 for 5 minutes raised the reflectance to 83%.

it was found, however, that the chlorine bleached fabric had the undesirable property of being discolored and tendered when exposed to moist heat. For example, a sample of the bleached fabric was placed in a Mason jar together with a small beaker containing 1 ml. water, the jar sealed and held at C. for 16 hours. After this treatment the reflectance of the samples had dropped to 57% and the fabric was badly tendered. The fabric was much more resistant to dry heat. A sample heated in an oven for 16 hours at 105 was not tendered and its reflectance was still 80%. Samples bleached with hydrogen peroxide instead of chlorine were similarly tendered on exposure to moist heat.

It was found that an after treatment of the cured fabric with caustic was effective in preventing the above described harmful efiects of moist heat. The treated fabric was padded through a solution of 50 grams of sodium hydroxide per liter, held at room temperature for 5 minutes, washed and then bleached as before in 1 g./l. chlorine solution at pH 10 for 5 minutes. After washing and pressing the fabric had a reflectance of 83.2% and a crease resistance of 247.

On exposure to moist heat for 24 hours the reflectance was 77% and the fabric was not tendered. It had a crease resistance of 247. This is very satisfactory.

Similarly an after treatment by padding through a solution of 250 grams 1421 50 111 0, holding for 5 minutes and washing was effective in preventing tendering by moist eat.

A sample of 80 x 80 white cotton fabric was padded through a solution containing 300 grams of the above diether product per liter. The pickup was 50%. The fabric was allowed to dry at room temperature, then padded through a 100 gram/liter caustic solution squeezed to pick up 50% and suspended to hang free for 15 minutes. The fabric was then washed free of caustic in hot water. The treated fabric had a high degree of crease resistance when wet and did not tenderizc or objectionally discolor under moist heat.

EXAMPLE 2 Ethylene Glycol Di (Beta-( Vinylsulfonyl)Ethyl) Ether A mixture was prepared from 6.21 grams of ethylene glycol (0.1 mole) and 23.6 grams (0.2 mole) of divinylsulfone. Sodium hydroxide in 10% solution was added dropwise until a rise in temperature indicated that an exothermic reaction had started. The maximum temperature reached was 38 C. After 16 hours the mixture was neutralized to pH 7 by adding acetic acid. The product thus obtained was analyzed for vinylsulfonyl group content and was found to contain about 50% of the amount of said groups in the original mixture. The product, ethylene glycol di(beta(vinylsulfonyl)ethyl)- ether, was water soluble, had only a slightly irritating odor and was considerably less noxious than divinylsulfone.

An 30 x 80 cotton fabric was padded with an aqueous solution of 100 grams of the diether as prepared above and 5 grams of sodium carbonate per liter. The pickup was 100%. The impregnated fabric was dried and cured in a forced draft oven at C., washed and pressed. It had a wet and dry crease recovery angle of 247. Another sample of the same fabric was first padded with 100 gram/ liter sodium hy roxidc, allowed to dry and then run through an aqueous solution containing 100 grams/liter of the diether, squeezed to 100% pickup and allowed to hang free for 15' minutes. It was then washed in hot water. The crease recovery angle of the wet fabric was 248 indicating a high wet crease resistance.

weight of about 600 and 23.6 grams (0.2 mole) of divinylsulfone and a sodium hydroxide solution was added dropwise thereto until a temperature rise indicated the beginning of the reaction. After 4 hours acetic acid was added to adjust to pH 7. The product obtained was analyzed for vinylsulfonyl group content and was found to contain 50% of the amount of said group originally present. The product, polyoxyethylene glycol (600 di- (beta-(vinylsulfonyl)ethyl) ether was water-soluble, only a slight irritating odor and was considerably less noxious than divinyl sulfone.

A strip of 80 x 80 cotton fabric, bleached and mercerized, was padded through an aqueous solution containing 200 grams of the diether as prepared above and 5 grams of sodium carbonate per liter. The pickup was 100%. The fabric was then dried and cured in a forced draft oven at 160 C. for four minutes, washed and then pressed. It had a wet and dry crease recovery angle of 225.

Another sample of the fabric was padded with 100 grams per liter of sodium hydroxide, allowed to dry and then run through an aqueous solution containing 200 grams/liter of the diether, squeezed to 100% pickup and allowed to hang free for minutes. It was then washed free of caustic. The crease recovery angle of the wet fabric was 214.

What is claimed is:

1. An addition product of one mole of an aliphatic glycol and approximately two moles of a divinylsnlfone having from one to two intermediate sulfonyl radicals, each of said radicals being linked to a terminal group at each end of said addition product molecule, said terminal group being from the class consisting of vinyl and mono-hydrocarbon substituted vinyl and having not more than eight carbon atoms.

2. An addition product of diethylene glycol and divinylsulfone having the formula:

3. An addition product of ethylene glycol and divinyl sulfone having the formula:

CH =CHSO CI-I CH OCH CH OCH CH SO CH=CH 4. Addition products of polyethylene glycol having an average molecular weight of about 600 and divinylsulfone having the formula:

5. The process of providing crease resistance to cellulosic textile fabrics comprising impregnating cellulosic textile fabrics with a solution of an addition product of about one mole of an aliphatic glycol and about two moles of a divinylsulfone having one to two intermediate sulfonyl radicals, each of said radicals being linked to a terminal group at each end of said addition product molecule, said terminal group being from the class consisting vinyl and mono-hydrocarbon substituted vinyl, and having not more than eight carbon atoms, and heat c the resulting impregnated fabric under alkaline 6. The process claimed in claim 5 wherein said addition product is ethylene glycol di(beta-(vinylsulfonyl)ethyl) ether.

7. The process claimed in claim 5 wherein said addi: tion product is diethylene glycol di(beta-(vinylsulfony1)- ethyl) ether.

8. The process claimed in claim 5 wherein said addition product is the di(beta-(vinylsulfonyl)ethyl) ether of polyethylene glycol having an average molecular Weight of about 600.

9. The process claimed in claim 5 wherein the fabric is thereafter treated with a material from the class consisting of strong alkali and a material which readily reacts with vinylsulfonyl groups.

10. The process claimed in claim 5 wherein the fabric is thereafter treated with sodium suliite.

11. The process of providing crease resistance to cellulosic textile fabric comprising treating said fabric with a strong alkali and a solution of addition product of one mole of an aliphatic glycol an imately two moles of a divinylsulione having from no to two intermediate sulfonyl radicals, each or" said radicals ing linked to a terminal group at each end of said a ion product molecule, said terminal group being from the class consisting of vinyl and mono-hydrocarbon substituted vinyl and having not more than eight carbon atoms.

12. The process claimed in claim 11 wherein the strong alkali is caustic.

' 13. Cellulosic textiles having an impregnation of the product claimed in claim 1 in hardened condition.

References Cited in the file of this patent UNITED STATES PATENTS 2,505,566 Shoene Apr. 25, 1950 2,524,399 Shoene et a1. Oct. 3, 1950 

5. THE PROCESS OF PROVIDING CREASE RESISTANCE TO CELLULOSIC TEXTILE FABRICS COMPRISING IMPREGNATING CELLULOSE TEXTILE FABRICS WITH A SOLUTION OF AN ADDITION PRODUCT OF ABOUT ONE MOLE OF AN ALIPHATIC GLYCOL AND ABOUT TWO MOLES OF A DIVINYLSULFONE HAVING ONE TO TWO INTERMEDIATE SULFONYL RADICALS, EACH OF SAID RADICALS BEING LINKED TO A TERRMINAL GROUP AT EACH END OF SAID ADDITION PRODUCT MOLECULE, SAID TERMINAL GROUP BEING FROM THE CLASS CONSISTING OF VINYL AND MONO-HYDROCARBON SUBSTITUTED VINYL, AND HAVING NOT MORE THAN EIGHT CARBON ATOMS, AND HEAT CURING THE RESULTING IMPREGNATED FABRIC UNDER ALKALINE CONDITIONS. 